钒钼杂多酸盐相转移催化环戊烯氧化制备戊二醛

doi:10.6023/cjoc202209027

摘要/Abstract

设计合成了一系列含高价态钼、钒等金属的杂多酸类相转移催化剂, 用于催化环戊烯(CPE)氧化制备戊二醛的反应, 筛选出催化活性最优的咪唑基钼钒酸盐催化剂[C₄H₉N₂C₃H₃(CH₃)]₅VMo₇O₂₆, 并对溶剂种类、H₂O₂用量、催化剂用量、反应温度、时间等进行了条件优化. 在优化的反应条件[V(乙酸乙酯)∶V(水)=4∶1, n(Cat.)∶n(H₂O₂)∶n(CPE)=1∶170∶41.6, 50 ℃, 6 h]下, 得到了88.7%的环戊烯转化率和62.1%的戊二醛选择性, 并且催化剂在经过7次循环使用后仍能保持较高的催化活性.

关键词: 过氧化氢, 环戊烯, 戊二醛, 相转移催化, 杂多酸离子液体

A series of heteropolyacid phase transfer catalysts containing high-valent molybdenum, vanadium and other metals were designed and synthesized to catalyze the oxidation of cyclopentene to glutaraldehyde, and the best imidazolyl molybdate-vanadate catalyst [C₄H₉N₂C₃H₃(CH₃)]₅VMo₇O₂₆ was screened out. The conditions of solvent type, H₂O₂ dosage, catalyst dosage, reaction temperature and time were optimized. Under the optimized reaction conditions [V(ethyl acetate)∶V(water)=4∶1, n(Cat.)∶n(H₂O₂)∶n(CPE)=1∶170∶41.6, 50 ℃, 6 h], 88.7% cyclopentene conversion and 62.1% glutaraldehyde selectivity were obtained, and the catalyst still maintained high catalytic activity after 7 cycles of use.

Key words: hydrogen peroxide, cyclopentene, glutaraldehyde, phase transfer catalysis, heteropolyacid ionic liquid

引用此文

张旭征, 于凤丽, 袁冰, 解从霞, 于世涛. 钒钼杂多酸盐相转移催化环戊烯氧化制备戊二醛[J]. 有机化学, 2023, 43(4): 1444-1451.

Xuzheng Zhang, Fengli Yu, Bing Yuan, Congxia Xie, Shitao Yu. Phase Transfer Catalytic Oxidation of Cyclopentene to Glutaraldehyde by Vanadium Molybdenum Heteropolyacid Salts[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1444-1451.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 13

Entry	Catalyst	Acid strength/mV	Conversion/%	Selectivity/%
Entry	Catalyst	Acid strength/mV	Conversion/%	Glutaraldehyde	Cyclopentanediol	Others
1			2
2	[C₆H₁₃NC₅H₅]₄Mo₈O₂₆	145	58.5	32.4	40.1	27.5
3	[C₆H₁₃NC₅H₅]₃HMo₈O₂₆	158	52.0	31.3	40.5	28.2
4	[C₆H₁₃NC₅H₅]H₃Mo₈O₂₆	209	55.9	30.7	45.2	24.1
5	[C₆H₁₃NC₅H₅]₅VMo₇O₂₆	24	83.2	51.6	43.7	4.7
6	[C₄H₉N₂C₃H₃(CH₃)]₅VMo₇O₂₆	34	88.7	62.1	32.2	5.7
7	[C₂H₅N₂C₃H₃(CH₃)]₅VMo₇O₂₆	37	77.9	57.1	30.3	12.6
8	[C₈H₁₇N₂C₃H₃(CH₃)]₅VMo₇O₂₆	29	90.1	61.3	34.5	4.2

表1. 不同催化剂对催化性能的影响a

Table 1. Effects of different catalysts on the catalytic performance

图1. 催化剂[C4H9N2C3H3(CH3)]5VMo7O26反应前后的FT-IR光谱

Figure 1. FT-IR spectra of catalyst [C4H9N2C3H3(CH3)]5VMo7- O26 before and after reaction

图2. 催化剂[C4H9N2C3H3(CH3)]5VMo7O26的1H NMR

Figure 2. 1H NMR spectrum of the catalyst [C4H9N2C3H3(CH3)]5VMo7O26

图3. 催化剂[C4H9N2C3H3(CH3)]5VMo7O26的TG曲线

Figure 3. TG curve of the catalyst [C4H9N2C3H3(CH3)]5VMo7- O26

图4. 催化剂[C4H9N2C3H3(CH3)]5VMo7O26的XRD谱图

Figure 4. XRD spectrum of the catalyst [C4H9N2C3H3(CH3)]5V- Mo7O26

Ethyl acetate/mL	Water/mL	CPE conversion/%	GA selectivity/%
5	0	89.1	47.2
4	1	88.5	61.9
3	2	83.0	55.2
2	3	78.2	53.6
1	4	70.6	44.1

表2. 不同油/水比对反应的影响a

Table 2. Influence of different oil/water ratios on the reaction

图5. 过氧化氢用量对反应的影响

Figure 5. Influence of hydrogen peroxide dosage on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, 45 ℃, 6 h

图6. 催化剂用量对反应的影响

Figure 6. Influence of the catalyst dosage on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, n(Cat.)∶n(H2O2)∶n(CPE)=1∶170∶41.6, 45 ℃, 6 h

图7. 反应温度对反应的影响

Figure 7. Influence of reaction temperature on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, n(Cat.)∶n(H2O2)∶n(CPE)=1∶170∶41.6, 6 h

图8. 反应时间对反应的影响

Figure 8. Influence of reaction time on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, n(Cat.)∶n(H2O2)∶n(CPE)=1∶170∶41.6, 45 ℃, 6 h

图9. 催化剂在反应中的可重复使用性

Figure 9. Reusability of the catalyst on the reaction Reaction conditions: 4 mL of ethyl acetate and 1 mL of water, n(Cat.)∶n(H2O2)∶n(CPE)=1∶170∶41.6, 45 ℃, 6 h

图10. 环戊烯反应体系的连续在线FT-IR光谱

Figure 10. Continuous on-line FT-IR spectra of cyclopentene reaction system Reaction time: a, 0 min; b, 5 min; c, 10 min; d, 15 min; e, 20 min; f, 25 min; g, 30 min

图式1. CPE选择性氧化成GA的可能反应机理

Scheme 1. Possible reaction mechanism of CPE selective oxidation to GA

参考文献 16

[1]	(a) Song, X. Y.; Guo, J. W.; Cui, Y. D.; Zhang, K. Fine Petrochem. 1999, 16, 46. (in Chinese)
	(宋晓锐, 郭建维, 崔英德, 张昆, 精细石油化工, 1999, 16, 46.)
	(b) Jiang, Z. H. Petrochem. Ind. Appl. 2009, 28, 8. (in Chinese)
	(江镇海, 石油化工应用, 2009, 28, 8.)
	(c) Jiang, Z. H. Shanghai Chem. Ind. 2009, 34, 33. (in Chinese)
	(江镇海, 上海化工, 2009, 34, 33.)
[2]	(a) Li, X. C.; Chen, J. F.; Li, S. Y.; Zhang, Z. Z. Chem. Ind. Eng. Prog. 2002, 22, 222. (in Chinese)
	(李兴存, 陈进富, 李术元, 张忠智, 化工进展, 2002, 22, 222.)
	(b) Li, Y.; Zhang, C. P. Chem. Intermed. 2002, 2, 8. (in Chinese)
	(刘颖, 张传平, 化工中间体, 2002, 2, 8.)
	(c) Chen, M. M.; Fang, Y. X.; Zhang, Y. C. Guangzhou Chem. Ind. 2003, 31, 51. (in Chinese)
	(陈敏敏, 方岩雄, 张永成, 广州化工, 2003, 31, 51.)
	(d) Zhang, X. X.; Song, Y. Y.; Li, M. Chem. Technol. Mark. 2005, 28, 13. (in Chinese)
	(张学旭, 宋云英, 李明, 化工科技市场, 2005, 28, 13.)
	(e) Hao, C. L. Chem. Technol. Mark. 2010, 33, 38. (in Chinese)
	(郝春来, 化工科技市场, 2010, 33, 38.)
[3]	(a) Yan, Q. D.; Gao, J. R. Chem. Times 2007, 21, 57. (in Chinese)
	(闫启东, 高建荣, 化工时刊, 2007, 21, 57.)
	(b) Qian, B. Z.; Zhu, J. F. Petrochem. Technol. Appl. 2008, 26, 86. (in Chinese)
	(钱伯章, 朱建芳, 石化技术与应用, 2008, 26, 86.)
[4]	(a) Jin, R.; Xia, X.; Dai, W.; Deng, J. F.; Li, H. Catal. Lett. 1999, 62, 201. doi: 10.1023/A:1019094905328
	(b) Jin, R.; Xia, X.; Xue, D.; Deng, J. F. Chem. Lett. 1999, 28, 371. doi: 10.1246/cl.1999.371
	(c) Chen, H.; Dai, W. L.; Deng, J. F. Catal. Lett. 2002, 81, 131. doi: 10.1023/A:1016032711528
[5]	Wu, P. Ph.D. Dissertation, Hebei University of Technology, Shijiazhuang, 2013. (in Chinese)
	(吴鹏, 博士论文, 石家庄, 河北科技大学,2013.)
[6]	Zhang, J.; Mai, J.; Chen, J.; Wang, X.; Mai, Y. ChemistrySelect 2022, 7, 4.
[7]	(a) Furukawa, H.; Nakamura, T.; Inagaki, H. Chem. Lett. 1988, 17, 877. doi: 10.1246/cl.1988.877
	(b) Lee, K. Y.; Itoh, K.; Hashimoto, M.; Mizuno, N.; Misono, M. Stud. Surf. Sci. Catal. 1994, 82, 583.
[8]	Amarasekara, A. S. Chem. Rev. 2016, 116, 6133. doi: 10.1021/acs.chemrev.5b00763 pmid: 27175515
[9]	(a) Wang, Z. N.; Wang, J. Y.; Si, Y. H. Chem. Ind. Eng. Prog. 2008, 28, 1057. (in Chinese)
	(王仲妮, 王洁莹, 司友华, 化学进展, 2008, 28, 1057.)
	(b) Zhang, S. J.; Liu, X. M.; Yao, X. Q. Sci. China, Ser. B: Chem. 2009, 39, 1134. (in Chinese)
	(张锁江, 刘晓敏, 姚晓倩, 中国科学B辑: 化学, 2009, 39, 1134.)
	(c) Jiang, P. P.; Li, X. T.; Leng, Y.; Zhang, P. B. Chem. Ind. Eng. Prog. 2014, 33, 2815. (in Chinese)
	(蒋平平, 李晓婷, 冷炎, 张萍波, 化工进展, 2014, 33, 2815.)
[10]	Ding, Y. N.; Xie, C. X.; Yu, F. L. Chem. Bull. 2019, 82, 231. (in Chinese)
	(丁亚男, 解从霞, 于凤丽, 化学通报, 2019, 82, 231.)
[11]	Zhang, C. J.; Liu, X.; Cui, G. N.; Dong, L. M.; Sui, F. Y.; Pang, H. J. Mol. Struct. 2022, 8, 15.
[12]	Verma, S.; Joshi, A.; De, S. R.; Jat, J. L. New J. Chem. 2021, 46, 2005. doi: 10.1039/D1NJ04950J
[13]	Qi, Y.; Han, Q.; Wu, L.; Li, J. New J. Chem. 2021, 45, 19264. doi: 10.1039/D1NJ02427B
[14]	Raj, N. K. K.; Ramaswamy, A. V.; Manikandan, P. J. Mol. Catal. A: Chem. 2005, 277, 37.
[15]	Zhou, M. D.; Liu, M. J.; Huang, L. L. Green Chem. 2014, 17, 1186. doi: 10.1039/C4GC01411A
[16]	Krivosudský, L.; Roller, A.; Rompel, A. Acta Crystallogr., Sect. C: Struct. Chem. 2019, C75, 872.